Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X‑ray Transient Absorption Spectroscopy

Aditi Bhattacherjee; Kirsten Schnorr; Sven Oesterling; Zheyue Yang; Tian Xue; Regina de Vivie-Riedle; Stephen R Leone

doi:10.1021/jacs.8b07155

Journal article

Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X‑ray Transient Absorption Spectroscopy

Aditi Bhattacherjee, Kirsten Schnorr, Sven Oesterling, Zheyue Yang, Tian Xue, Regina de Vivie-Riedle and Stephen R Leone

Journal of the American Chemical Society, Vol.140(39), pp.12538-12544

10/03/2018

DOI: 10.1021/jacs.8b07155

PMID: 30204442

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https://www.osti.gov/servlets/purl/1580334View

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Abstract

The ultraviolet-induced photochemistry of five-membered heterocyclic rings often involves ring opening as a prominent excited-state relaxation pathway. The identification of this particular photoinduced mechanism, however, presents a challenge for many experimental methods. We show that femtosecond X-ray transient absorption spectroscopy at the carbon K-edge (∼284 eV) provides core-to-valence spectral fingerprints that enable the unambiguous identification of ring-opened isomers of organic heterocycles. The unique differences in the electronic structure between a carbon atom bonded to the oxygen in the ring versus a carbon atom set free of the oxygen in the ring-opened product are readily apparent in the X-ray spectra. Ultrafast ring opening via C–O bond fission occurs within ∼350 fs in 266-nm photoexcited furfural, as evidenced by fingerprint core (carbon 1s) electronic transitions into a nonbonding orbital of the open-chain carbene intermediate at 283.3 eV. The lack of recovery of the 1sπ* ground-state depletion in furfural at 286.4 eV indicates that internal conversion to the ground state is a minor channel. These experimental results, augmented by recent advances in the generation of isolated attosecond pulses at the carbon K-edge, will pave the way for probing ring-opened conical intersection dynamics in the future.

Details

Title: Subtitle: Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X‑ray Transient Absorption Spectroscopy
Creators: Aditi Bhattacherjee - Lawrence Berkeley National Laboratory
Kirsten Schnorr - Lawrence Berkeley National Laboratory
Sven Oesterling - Department of Chemistry
Zheyue Yang - Lawrence Berkeley National Laboratory
Tian Xue - Lawrence Berkeley National Laboratory
Regina de Vivie-Riedle - Department of Chemistry
Stephen R Leone - Department of Physics
Resource Type: Journal article
Publication Details: Journal of the American Chemical Society, Vol.140(39), pp.12538-12544
DOI: 10.1021/jacs.8b07155
PMID: 30204442
NLM abbreviation: J Am Chem Soc
ISSN: 0002-7863
eISSN: 1520-5126
Publisher: American Chemical Society
Grant note: DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-AC02-05CH11231; DOI: 10.13039/501100001659, name: Deutsche Forschungsgemeinschaft, award: SFB749; DOI: 10.13039/501100001663, name: Volkswagen Foundation
Language: English
Date published: 10/03/2018
Academic Unit: Chemistry
Record Identifier: 9984216593202771

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